Glyceryl silicone ester emulsifiers

ABSTRACT

The invention discloses novel ester emulsifiers. Compounds of the invention are made by reacting (a) a carboxy silicone, and (b) a glycerine which has been substituted with a fatty group containing 4 to 20 carbon atoms. The compounds of the invention by virtue of (i) the silicone group, (ii) the fatty group and (iii) the polyoxyalkylene present in the compound are extremely efficient emulsifiers for a variety of oils at heretofore unknown levels.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention discloses novel ester emulsifiers. Compounds of theinvention are made by reacting (a) a carboxy silicone, and (b) aglycerine which has been substituted with a fatty group containing 4 to20 carbon atoms. The compounds of the invention by virtue of (i) thesilicone group, (ii) the fatty group and (iii) the polyoxyalkylenepresent in the compound are extremely efficient emulsifiers for avariety of oils at heretofore unknown levels.

The esterification by which the compounds are prepared is the reactionof a carboxy silicone, which may contain varying amounts ofpolyoxyalkylene in the molecule, and a glyceryl ester.

2. Arts and Practices

Silicone compounds have been known to be active at the surface ofplastic, cellulosic and synthetic fibers as well as paper. They are goodnondurable lubricants and are very stable to oxidation, however, theirhigh cost and lack of efficiency at low concentrations as well as lowdurability have made their acceptance in commercial products quite low.In all instances, commercially available quaternaries are the activeingredient in traditional laundry care markets, with little or nosilicone added.

The low efficiency and low durability of dimethylpolysiloxane is due tothe fact that it is very water insoluble and deposits on the surface toobtain a minimum free energy in the solution. Simply, the silicone oildelivery to the surface by hydrophobic binding, not chemical bonding. Atthe surface, the dimethylpolysiloxane is a very effective fiberlubricant, however, there are two drawbacks, first; thedimethylpolysiloxane is not chemically bonded so the effect is verytransient and disappears with one washing, and second; since there is noreaction of the dimethylpolysiloxane to the surface an equilibriumbetween fiber absorbed dimethylpolysiloxane and dimethylpolysiloxane inthe dispersion results in very inefficient percentage of siliconedeposited. A large amount of the expensive silicone goes down the drainwith the waste water.

In many applications, there is a strong desire to obtain a solid waxwhich can be used in applications were a spread on application is ofinterest. These applications include personal care applications likeantiperspirants and skin creams. Unfortunately most silicone derivativesare liquid to very low temperatures. Attempts to overcome thisdeficiency have been made by reacting stearyl alcohol with achlorosilane. The difficulty with the use of this type of material isthat a large excess (50% by weight) of the alcohol needs to be added toget a product which is free of the irritating chlorosilane raw material.When such an excess is used the product behaves functionally more likethe stearyl alcohol than like a silicone compound. Additionally, thecompound is not polymeric, hence the superior lubrication andhydrophobicity enhancements which can be achieved bydimethylpolysiloxane is not obtainable with these compounds.

U.S. Pat. No. 3,511,699 to Sterman issued May 12, 1970 teaches thatepoxy compounds placed in the silicone backbone by hydrosilation can becured onto certain fibers to give improved substantivity. Thesubstantivity is based upon the reaction of hydroxyl groups on thecellulosic and the epoxy group in the silicone polymer. The resultingbond is a ether linkage and a new hydroxyl group. While a definiteimprovement over other compounds the efficiency and durability of thewere not good enough to allow for cost effective incorporation of thesematerials in detergent formulations.

U.S. Pat. No. 5,296,625 to O'Lenick teaches the preparation of thecarboxy silicone polymers which are raw materials useful in thereparation of the compounds of the present invention. This patent isincorporated herein by reference.

THE INVENTION OBJECT OF THE INVENTION

It is the object of the present invention to provide emulsifiers whichare effective at very low concentrations. These emulsifiers areeffective for making emulsions of various oily materials including butnot limited to triglycerides, silicone oil, mineral oil and fattyesters.

The formation of oil in water emulsions results in the placing of theoil in a micelle. The concentration of emulsifier needed to make amicelle stable is an important variable in the ability to deliver theoil to a substrate being tested. For example, if it is the desire todeliver silicone oil to a textile substrate from aqueous emulsion, it isdesirable to deliver as much of the oil from the micelle efficiently tothe surface. The greater the concentration of emulsifier, the greaterthe micelle will resist delivering the oil contained therein. Theundelivered oil in the emulsion goes down the drain, and is wasted. Itis therefore very desirable to develop an emulsifier which gives stableemulsions but is present in minimal concentration so as to allow forthrough and efficient delivery of the oil to the substrate beingtreated. The compounds of the present invention are such compounds. Theyare effective emulsifiers at concentrations as low as 0.05 %.

The incorporation of the fatty substituted glycerine into the siliconemolecule results in the improved the efficient emulsification.

SUMMARY OF THE INVENTION

The present invention relates to novel glyceryl fatty silicone estercompounds. Compounds of the invention by virtue of (a) the ester group,(b) the fatty glyceryl groups and (c) the polyoxyalkylene portion of themolecule present in the carboxy silicone are extremely efficientemulsifiers for a variety of oils. The emulsions give a good pay offwhen applied to substrate, that is they efficiently deliver the oil fromthe micelle, allowing the oil to spread out when applied to a variety ofsubstrates including hair, skin, wood, plastic and textile fibers. Thecompounds of the present invention are prepared by reacting a carboxysilicone compound with a glyceryl ester.

The compounds of this invent ion are made by the esterification of acarboxy silicone compound and a fatty glyceryl ester. Specifically, thecompounds of the present invention are esters compounds which isprepared by the esterification reaction of; (a) a silicone carboxylateconforming to the following structure: ##STR1## wherein; Me is methyl;

R and R' are CH₃ or --(CH₂)₃ --O--(EO)_(a) --(PO)_(b) --(EO)_(c)--C(O)--R"--C(O)--OH; with the proviso that both R and R' are not CH₃ ;

R" is selected from --CH₂ --CH₂ --; --CH═CH--; --CH₂ --C⁷ (R)--H;##STR2## R⁷ is alkyl having from 1 to 20 carbon atoms; R¹ is selectedfrom lower alkyl CH₃ (CH)_(n) --or phenyl;

n is an integer from 0 to 8;

a, b and c are integers independently ranging from 0 to 20;

EO is an ethylene oxide residue --(CH₂ CH₂ --O)--;

PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--;

o is an integer ranging from 1 to 100;

q is an integer ranging from 0 to 500. and

(c) a glyceryl ester conforming to the following structure; ##STR3##wherein;

p. 8

R is --C(O)--R"

R' is selected from the group consisting of R or H;

R" is CH₃ --(CH₂)_(n) --

n is ranges from 3 to 19.

The carboxy silicone compounds useful as raw materials in thepreparation of the compounds of the present invention are disclosed inU.S. Pat. No. 5,296,625 to O'Lenick, Jr. et al, incorporated herein byreference.

The compounds of the present invention conform to the followingstructure: ##STR4## wherein; R is --C(O)--R"

R³ is selected from the group consisting of R or R² ;

R" is CH₃ --(CH₂)_(n) --

n is ranges from 3 to 19.

R² is: ##STR5## wherein; Me is methyl;

R¹ is selected from lower alkyl CH₃ (CH)_(n) -- or phenyl;

n is an integer from 0 to 8;

R⁵ and R⁴ are CH₃ or --(CH₂)₃ --O--(EO)_(a) --(PO)_(b) --(EO)_(c)--C(O)--R⁶ --C(O)--; with the proviso that both R⁵ and R⁴ are not CH₃ ;

R⁶ is selected from --CH₂ --CH₂ --; --CH═CH--; --CH₂ --C(R⁷)--H;##STR6## R⁷ is alkyl having from 1 to 20 carbon atoms; a, b and c areintegers independently ranging from 0 to 20;

EO is an ethylene oxide residue --(CH₂ CH₂ --O)--;

PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--;

o is an integer ranging from 1 to 100;

q is an integer ranging from 0 to 500;

REFERRED EMBODIMENTS

In another preferred embodiment x+y+z is greater than zero.

In another preferred embodiment n ranges from 3 to 11.

In another preferred embodiment n is 3.

In another preferred embodiment n is 5.

In another preferred embodiment n is 7.

In another preferred embodiment n is 9.

In another preferred embodiment n is 11.

In another preferred embodiment n is 13.

In another preferred embodiment n is 15.

In another preferred embodiment n is 17.

In another preferred embodiment n is 19.

EXAMPLES

The compounds of the present invention are prepared by the reaction of acarboxy silicone compound and a glyceryl ester. Examples of suitablereactants are as follows;

Reactants Glyceryl Esters

Glyceryl Esters are commercially available from a variety of suppliers,onesupplier is Ethox Chemical of Spartanburg S.C. They conform to thefollowing structure; ##STR7##wherein; R is --C(O)--R"

R' is selected from the group consisting of R or H;

R" is CH₃ --(CH₂)_(n) --

n is ranges from 3 to 19.

    ______________________________________                                        Reactant Example                                                              Number             n Value  R.sup.1                                           ______________________________________                                        1                   3       H                                                 2                   7       H                                                 3                   9       H                                                 4                  11       H                                                 5                  13       H                                                 6                  15       H                                                 7                  17       H                                                 8                  19       H                                                 9                   3       R                                                 10                  7       R                                                 11                  9       R                                                 12                 11       R                                                 13                 13       R                                                 14                 15       R                                                 15                 17       R                                                 16                 19       R                                                 ______________________________________                                    

Dimethicone Carboxylate Compounds

Dimethicone Carboxylate compounds are disclosed in U.S. Pat. No.5,296,625 incorporated herein by reference. They marketed by Siltechunder the Silube trade name. The compounds conform to the followinggeneric structure; ##STR8##wherein; Me is methyl;

R and R' are CH₃ or --(CH₂)₃ --O--(EO)_(a) --(PO)_(b) --(EO)_(c)--C(O)--R6--C(O)--OH; with the proviso that both R and R' arenot CH₃ ;

R6 is selected from --CH₂ --CH₂ --; --CH═CH--; --CH₂ --C(R⁷)--H;##STR9##R⁷ is alkyl having from 1 to 20 carbon atoms; R¹ is selectedfromlower alkyl CH₃ (CH)_(n) -- or phenyl;

n is an integer from 0 to 8;

a, b and c are integers independently ranging from 0 to 20;

EO is an ethylene oxide residue --(CH₂ CH₂ --O)--;

PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--;

o is an integer ranging from 1 to 100;

q is an integer ranging from 0 to 500.

The carboxy reactants are defined in O'Lenick U.S. Pat. No. 5,296,625incorporated herein by reference, examples 15-32.

R6 Definition

I) O'Lenick Reactant Example I (Succinic Anhydride)

    R.sup.6 is --H.sub.2 C--CH.sub.2 --

II) O'Lenick Reactant Example II (Alkyl Succinic Arthydride)

R⁶ is ##STR10##

III) O'Lenick Reactant Example III (Alkyl Succinic Anhydride)

R⁶ is ##STR11##

IV) O'Lenick Reactant Example IV (Alkyl Succinic Anhydride)

R⁶ is ##STR12##

V) O'Lenick Reactant Example V (Alkyl Succinic Arthydride)

R⁶ is ##STR13##

VI) O'Lenick Reactant Example VI (Alkyl Succinic Anhydride)

R⁶ is ##STR14##

VII) O'Lenick Reactant Example VII (Maleic Anhydride)

    R.sup.6 is --HC═CH--

VIII) O'Lenick Reactant Example VIII (Phthalic Anhydride)

R⁶ is ##STR15##

IX) O'Lenick Reactant Example IX (Tetrachlorophthalic arthydride)

R⁶ is ##STR16##

Compounds of the Present Invention General Reaction Conditions

The esterification can be run without catalyst; however, when nocatalysts used reaction rates are less efficient. Standardesterification catalysts are generally used at concentrations of between0.05% to 0.50% with a preferred range of 0.1% to 0.3%. Catalysts whichare effective include butare not limited to; sulfuric acid, p-toluenesulfonic acid, methane sulfonic acid, tin metal, zinc metal, titaniummetal, organo titianares, organo tin compounds, organo zinc compounds,zinc oxide, magnesium oxide, calcium oxide, etc. The most preferredcatalyst is stannous oxylate. The reaction is conducted at between 140and 240 C. under an inert nitrogen blanket. The nitrogen blanketpreserves the color. Preferred temperature range is between 180 and 210C. Water is removed from the reaction which is done using a nitrogensparge or vacuum.

Examples 17-34 General Procedure

Into a suitable round bottom, three neck flask equipped with a DeanStark trap, a thermometer and a nitrogen sparge is added the specifiednumber ofgrams of the carboxy silicone and the specified number of gramsof glycerylester and 0.25 % of total weight of the batch of catalyst.The reaction mass is blanketed with nitrogen, and heated to 180 and 200C. under an inert nitrogen blanket. Once the reaction temperaturereaches 120 C. waterbegins to boil off and is collected in the DeanStark Trap. Within four to five hours the theoretical water is collectedoff and the acid value is very low. The product is used withoutadditional purification.

Example 17

Into a suitable round bottom, three neck flask equipped with a DeanStark trap, a thermometer and a nitrogen sparge is added the specifiednumber ofgrams of the carboxy silicone), 175.0 grams of Reactant Example1, (the glyceryl ester) and 0.25 % of total weight of the batch ofcatalyst. The reaction mass is blanketed with nitrogen, and heated to180 and 200 C. under an inert nitrogen blanket. Once the reactiontemperature reaches 120C. water begins to boil off and is collected inthe Dean Stark Trap. Withinfour to five hours the theoretical water iscollected off and the acid value is very low. The product is usedwithout additional purification.

Example 18-34

Example 17 is repeated only this time substituting the specified numberof grams of the specified carboxy silicone for the carboxy siliconespecifiedand the specified type and the specified type and number ofgrams of glyceryl ester compound as shown below;

Note; In the below table Gms. is grams

    ______________________________________                                        Carboxy Silicone Compound                                                     R.sup.6      O'Lenick          Glyceryl Ester                                 Example                                                                              Definition                                                                              Example  Grams  Example                                                                              Grams                                 ______________________________________                                        17     I         15       2,429.0                                                                              1      175.0                                 18     II        16       2,147.0                                                                              2      237.0                                 19     III       17       5,398.0                                                                              3      259.0                                 20     IV        18         533.0                                                                              4      287.0                                 21     V         19       4,723.0                                                                              5      315.0                                 22     VI        20       3,083.0                                                                              6      343.0                                 23     VII       21       3,648.8                                                                              7      371.0                                 24     VIII      22       1,722.4                                                                              8      399.0                                 25     IX        23       1,288.0                                                                              9      260.0                                 26     I         24       6,100.0                                                                              10     378.0                                 27     II        25       10,115.0                                                                             11     428.0                                 28     III       26       50,269.0                                                                             12     484.0                                 29     IV        27       86,185.0                                                                             13     540.0                                 30     V         28       2,6450 14     596.0                                 31     VI        29       2,372.0                                                                              15     652.0                                 32     VII       30       5,229.0                                                                              16     708.0                                 33     VIII      31         495.6                                                                              1      175.0                                 34     IX        32       4,695.0                                                                              10     378.0                                 ______________________________________                                    

The compounds of the present invention were found to be excellentemulsifiers for a variety of oil phases including but not limited tosilicone oil, soybean oil and mineral oil. The average usage levelranged from 0.5% to 1.0% which is far lower than the levels used oftraditional fatty emulsifiers. In addition to the use at low levels, theemulsifier also had an exceptionally good skin feel, leaving the skinsoft and lubricated. This multi-functional attributes of theemuslifier/emmolient is not found in traditional fatty emulsifiers.

What is claimed;
 1. A compound conforming to the following structure:##STR17## wherein; R is --C(O)--R"R³ is selected from the groupconsisting of R or R² ; R" is CH₃ --(CH₂)_(n) -- n is ranges from 3 to19; R² is: ##STR18## wherein; Me is methyl; R³ is selected from loweralkyl CH₃ (CH)_(n) -- or phenyl; n is an integer from 0 to 8; R⁵ and R⁴are CH₃ or --(CH₂)₃ --O--(EO)_(a) --(PO)_(b) --(EO)_(c) --C(O)--R⁶--C(O)--; with the proviso that both R⁵ and R⁴ are not CH₃ ; R⁶ isselected from --CH₂ --CH₂ --; --CH═CH--; --CH₂ --C(R⁷)--H; ##STR19## R⁷is alkyl having from 1 to 20 carbon atoms; a, b and c are integersindependently ranging from 0 to 20; EO is an ethylene oxide residue--(CH₂ CH₂ --O)--; PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--;o is an integer ranging from 1 to 100; q is an integer ranging from 0 to500.
 2. A compound of claim 1 wherein x+y+z is greater than zero.
 3. Acompound of claim 1 wherein n ranges from 3 to
 11. 4. A compound ofclaim 1 wherein n is
 3. 5. A compound of claim 1 wherein n is
 5. 6. Acompound of claim 1 wherein n is
 7. 7. A compound of claim 1 wherein nis
 9. 8. A compound of claim 1 wherein n is
 11. 9. A compound of claim 1wherein n is
 13. 10. A compound of claim 1 wherein n is
 15. 11. Acompound of claim 1 wherein n is
 17. 12. A compound of claim 1 wherein nis
 19. 13. A silicone ester compound which is prepared by theesterification reaction of;(a) a silicone carboxylate conforming to thefollowing structure: ##STR20## wherein; Me is methyl; R and R' are CH₃or --(CH₂)₃ --O--(EO)_(a) --(PO)_(b) --(EO)_(c) --C(O)--R"--C(O)--OH;with the proviso that both R and R' are not CH₃ ; R" is selected from--CH₂ --CH₂ --; --CH═CH--; --CH₂ --C(R⁷)--H; ##STR21## R⁷ is alkylhaving from 1 to 20 carbon atoms; R¹ is selected from lower alkyl CH₃(CH)_(n) -- or phenyl; n is an integer from 0 to 8; a, b and c areintegers independently ranging from 0 to 20; EO is an ethylene oxideresidue --(CH₂ CH₂ --O)--; PO is a propylene oxide residue --(CH₂CH(CH₃)--O)--; o is an integer ranging from 1 to 100; q is an integerranging from 0 to 500; and (c) a glyceryl ester conforming to thefollowing structure; ##STR22## wherein R is --C(O)--R" R' is selectedfrom the group consisting of R or H; R" is CH₃ --(CH₂)_(n) -- n isranges from 3 to
 19. 14. A compound of claim 13 wherein x+y+z is greaterthan zero.
 15. A compound of claim 13 wherein n ranges from 3 to
 11. 16.A compound of claim 13 wherein n is
 3. 17. A compound of claim 13wherein n is
 5. 18. A compound of claim 13 wherein n is
 7. 19. Acompound of claim 13 wherein n is
 9. 20. A compound of claim 13 whereinn is 11.